Lubricating oil compositions



3,116,249 LUBRlCATlNG 61L CQMP@SETEQN Hyman Rainer, El Cerrito, andArnold Ill. Doepel, Concord, Catlin, assignors to Shell @il Company, NewYork, N.Y., a corporation of Delaware No Drawing. Filed Dec. 23, 1950,Ser. No. 77 ,816 ll Claims. (Cl. 252-625) This invention relates toimproved hydrocarbon lubricants, and particularly to mineral lubricatingoil compositions which possess good detergency, antiwear, as well assludge, corrosion or rust inhibiting properties.

It is known that certain non-ash forming polymeri nitrogen-containingcompounds in which the nitrogencontaining group may be amino or amidogroups such as vinylpyridines or vinylpyrrolidones, function asdetergents when added in small amounts to lubricants such as minerallubricating oils. However, copolymers of this type have been found tolack wear inhibiting properties and are corrosive and under severeconditions of use such as under extreme temperatures and pressure andthey have been found to be shear unstable resulting in sludging andother undesirable side effects.

In order to overcome these defects, the art discloses'that the additionof basic polyvalent metal salts such as basic alkaline earth metalpetroleum sulfonates or aromatic carboxylates such as alkyl salicylatesimparts wear inhibiting properties to lubricants containing theabove-mentioned non-ash forming detergents. However, it has beenobserved that the problem of corrosion remains and unclesirable sideeifects such as sludging arises due to the apparent complexingtendencies between the nitrogen-containing polymer and the basic metalsalts.

It has now been discovered that excellent ash-free detergent lubricantsare provided having in addition wear and corrosion inhibiting propertiesas well as being resistant towards sludging tendencies, by dispersing inlubricating oils such as mineral lubricating oils containing polymericnitrogen-containing detergents, a small amount of an oil-solubleN-amino-alkyl substituted irnidazoline salt or complex of an alkyl acidphosphate or phosphonate or its thio derivative. The salt or complex maybe represented by the formula 1 i Y (Y) R T where R is an alkyl orallcenyl group having from to 30 carbon atoms, R is hydrogen, a lower Calkyl radicar or mixtures of hydrogen and C kyl radicals, R" is ahydrocarbyl radical, e.g., an alkyl or chloroalkyl radical, X is anamino allzyl or polyamino polyl alkylene radical, e.g., -CH CH --NH{CH2CH2NH where x is an integer of from 1 to 4, Y is oxygen and/orsulfur, preferably oxygen and n can be Zero or one, preferably one.

The detergent nitrogen-containing polymers useful in compositions of thepresent invention include copolymers of monomers having polymerizedlinkages and containing nitrogen-containing groups which may be amino oramido groups. They may be derived from polymerizable monomers containingprimary, secondary or tertiary (the latter two are preferred) aminonitrogen, including heterocyclic amino or amido nitrogen-containingsubstances, having an ethylenically unsaturated polymerizable group.These detergent polymers may be obtained by polymerizing vinylsubstituted heterocyclic nitrogen-containing substances atent 'ice suchas vinyl pyridine, vinyl picoline and vinyl quinoline, vinyl pyrrolidoneor vinyl arylamines such as paraaminostyrene, or polyamines prepared byreducing, in the presence of ammonia or primary or secondary amines,with polymerizable unsaturated alcohols, acids or esters such asacrylates and methacrylates of long chain fatty cids, and the like. Thepreferred polymeric amino or amido compounds are those containingtertiary amine groups and particularly those containing heterocyclicamino groups such as obtained by copolymerizing a polymerizableheterocyclic nitrogen base compound-with a polymerizable unsaturatedmaterial free of heterocyclic nitrogen-containing radicals such as aredescribed in British patent specification 76'0,544 and US. Patents2,839,512 and 2,889,282. The copolymers include: copolymer of stearylmethacrylate and Z-methyl-S-vinyl pyridine; copolymer of stearylmethacrylate, lauryl :methacrylate and 2-me-thyl-5-vinyl pyridine; andthose which contain additional C alkyl methacrylates in the polymer,such as copolymers of stearyl methacrylate, lauryl methacrylate, methylmethacrylate and 2-methyl-5-vinyl pyridine; and similar copolymers inwhich the methyl methacrylate is replaced by butyl methacrylate and2-methyl-5-vinyl pyridine is replaced by 5-ethyl-2-vinyl pyridine; orcopolymers of lauryl methacrylate and N-vinyl pyrrolidone or similarcopolymers as described in Belgian Patent 550,442 and British Patent808,664, and mixtures thereof. Acrylate-vinyl pyrrolidone copolymers aresold by Rohm and Haas under the designations Acryloid 315X or 917 or 966and are copolymers of N-vinyl pyrrolidone and lauryl methacrylatc ofvarying molecular weights. Other suitable polymeric amines are thoseavailable commercially such as those sold by E. I. du Pont de Nemoursand Co. under the designations LOA 564 and 565, which are copolymers oflauryl methacrylate and diethylaminoethylmethacrylate described in US.Patent 2,737,496.

Particularly those preferred detergent polymers are the Acryloid 917 or966 copolymer (copolymer of lauryl methacrylate, N-vinyl pyrrolidone,M.W.=600,000) or the copolymers of vinyl pyrridine and mixtures ofdissimilar me'thacrylate esters, the preparation of which is illustratedby the following examples.

EXAMPLE I A mixture of 25% of 2-methyl-5-vinyl pyridine and stearylmethacrylate were heated in a 50-50 mixture of benzene and a lightmineral oil (East Texas SSU at 100 F. neutral) to about C. at which time0.25% wt. of ditertbutyl peroxide was added and the reaction mixture wasmaintained at this temperature for about 6 hours.

At the completion of the reaction, the solvent was stripped off and thepolymer diluted with neutral oil to a polymer content of about 30% byweight and filtered at l00120 C. The copolymer had a molecular weight ofabout 200,000 and a nitrogen content of 2.94%.

EXAMPLE ll 30% stearyl methacrylate, 51% lauryl methacrylate, 14% methylmethacrylate and 5.0% 2-metnyl-5-vinyl pyridine were charged to a300-gallon stainless steel autoclave. A 50-50 mixture of benzene andneutral petroleum oil was then added to the autoclave so as to furnish 1part of the mixture per 3 parts of the total monomer. 0.25% ofditertbutyl peroxide was then added and the mixture heated at 120 C. forabout 7 hours.

At the completion of the reaction, the benzene was stripped oil toconditions of 120 C. and 10 mm. Hg with nitrogen purging. Thebenezene-free product was then diluted with neutral oil to a polymercontent of about 30% by weight and filtered at l00 -l20 C. The polymer 3had a molecular weight of about 600,000 and a nitrogen content of 0.54%.

The wear and corrosion inhibitor for the above detergents andrepresented by Formula I above can be readily prepared by reacting molefor mole in a neutral vehicle such as a liquid hydrocarbon or mineraloil at between room temperature and 100 C., preferably at the lowertemperature, e.g., from room temperature to 60 C. an N-aminoalkylsubstituted imidazoline and an acid phosphate or phosphonate.

The imidazolines are well known compounds which may be prepared by themethods described in Chemical Reviews, vol. 54, No. 4, August 1954,under the title The Chemistry of Imidazoles, by Ferm and Riebsomer orthey may be prepared by the method described in Us. Patent 2,267,965.Examples of suitable compounds are l-aminoethyl-2-undecyl imidazoline,l-aminoethyl-Z- heptadecenyl imidazoline, l-aminoethyl-2-heptadecylimidazoline, l-aminoethylethylimino-2-heptadecyl imidazoline,1-aminoisopropyl-Z-heptadecyl-S-methyl imidazoline, l-aminobutyl 2pentadecyl imidazoline, 1-[2-(2-aminoethyl)-aminoethyl]-2-pentadecylimidazoline. Aminoalkyl substituted imidazolines of this type arecommercially available and are sold by The National AluminateCorporation under the trade name of Nalcarnines such as Nalcamine (3-32which is 1-(2-aminoethyl)-2-n- C aliryl imidazoline. Another preferredaminoalkyl imidazoline is prepared by reacting polyethylene polyaminewith tall oil acids under reaction condition (125- 250 C.) to producethe aminoalkyl imidazoline. A polyamine particularly desirable is amixture containing between 20 and 80% by weight of diethylene triamineor triethylene tetrarnine as a diluent, the remaining polyethylenepolyamines being those starting with tetraethylene pentamine and relatedhigher polymers having increasing complexity in structure and molecularweight.

The mixture of high molecular weight polyethylene polyamines is normallyobtained as a bottoms product in the process for the preparation ofethylene diamine. Consequently, it normally constitutes a highly complexmixture and even may include small amounts (less than about 3% byweight) of oxygenated materials. A typical mixture of polyethylenepolyamine diluted with about by weight of diethylene triamine has thefollowing analys1s:

Percent by weight carbon 51.5 Percent by weight nitrogen 34.3 Percent byweight hydrogen 11.6 Percent by weight oxygen 2.5 Total basicity,equivalents per 100 grams 1 1.98 Active nitrogen 81% Amine types,equivalents per 100 grams:

Primary 1.20

Tertiary 0.30 Specific gravity at 25 C 0.995-l.020 Viscosity centipoises75-250 Equivalent weight 42.5-47.5

Equivalent to 27.7% nitrogen.

The fatty acids to be utilized for the formation of imidazolines withthe polyethylene polyamines should have from 10 to about 22 carbon atomsper molecule and preferably from 17 to 19 carbon atoms, if at least 50%by weight of the acid are unsaturated and from 10 to 16 carbon atoms permolecule if the acids are substantially saturated. The product therebyformed may be either liquid or solid depending in part upon the degreeof saturation of the acids employed. In order to form a product which isliquid at the temperatures involved, it is desirable to utilize amixture of fatty acids wherein at least 50% by weight of the mixturecomprises acids having at least one double bond per molecule. Still morepreferably, at least 85% by weight of the fatty acids contain doublebonds and may have either one or two double bonds per molecule. Stearicacid may form a member of the mix- UNSATURATED, LOl/V COST FATTY ACIDIVIIXTURES Trade Name Standard Bone Tall Yellow Greasc Oleie Acid FattyAcid Residue. Tall Oil Fatty Acid Tall Oil Fatty Acid Crude Tall Oil lDistilled Tall Oil Iodine Sap. No.,

No. mg. KOII This product will be hereinbelow referred to asTalimidazoline.

The acid portion of the salt or complex include hydrocarbyl acidphosphates, e.g., mono and dialkyl, mono and dicycloalkyl, diaralkyl,diaryl, alkyl aryl, aralkyl alkyl acid phosphates and their thioderivatives having from 8 to 30 carbon atoms in the molecule. Examplesof suitable mono and di-acid and/or thio acid phosphates are mono anddioctyl acid phosphate, mono and dilauryl acid phosphate, mono anddistearyl acid phosphate, mono and dioleyl acid phosphate, mono anddicyclohexyl acid phos phate, dicresyl acid phosphate, lauryl cresylacid phosphate, dibenzyl acid phosphate, lauryl benzyl acid phosphate,dilauryl acid dithio phosphate, dilauryl thiono acid phosphate; alkylacid phosphonates such as monobutyl chloromethyl phosphonate, monolaurylchloromethyl phosphonate and the like. A preferred alkyl acid phosphateis Lorol acid phosphate, which is a mixture of phosphoric esters ofLorol alcohol. The term Lorol alcohol is used in the trade to denote amixture of primary normal aliphatic alcohols of 8 to 12 carbon atomswhich are obtained by fractionation of the alcohols resulting from thereduction of cocoanut and/or palm kernel oils. Lorol acid phosphatemixtures are readily obtainable on the market and for this reason arepreferred to the purified esters of greater scarcity and higher price.One Lorol acid phosphate type is sold under the trade name Ortholeum 162and is understood to be mainly a mixture of the mono and diacidphosphates of Lorol alcohol.

Examples of salts or complexes are l) Nalcamine G- 32 dilaurylphosphate, (2) Talimidazoline dilauryl phosphate, (3l-aminoethyl-2-heptadecyl imidazoline dilauryl phosphate, (4)l-aminoethyl-Z-heptadecyl imidazoline dioleyl phosphate, (5)l-aminoethyl-2-undecyl imidazoline distearyl phosphate, (6)1-(2-aminoethyl)aminoethyl-Z-pentadecyl imidazoline dilauryl phosphate,(7) l-aminoethy -2-heptadecyl imidazoline dicresyl phosphate, (8) 1aminoethyl-Z-heptadecyl imidazoline dithiodilauryl phosphate, (9)1-a1ninoisopropyl-2-pentadecyl imidazoline lauryl cresyl phosphate, (10)l-aminoethyI-Z-heptadecyl imidazoline monobutylchloromethyl phosphonateand mixtures thereof.

Additional improvement of oil compositions containing the above twoadditives of the present invention, namely the polymericnitrogen-containing detergent and imidazoline salt, particularly withrespect to oxidation and storage stability is accomplished by additionof small amounts of alkylated bisphenols having the general formula:

II O 011 (II) and preferably having the formula:

R stands for methyl or ethyl and n stands for an integer R from 1 to 3and wherein in (111) X is CH or sulfur and R is a tertiary alkylradical. The most preferred alkylated bisphenols are represented byFormula 111 those having a sulfur bridge or, and most especially, amethylene bridge and where R is tertiary butyl radical.

The alkylated bisphenols may contain from 1 to 8 alkyl groups, butpreferably they contain from 2 to 6 allayl groups. Alkylated bisphenolshaving 4 alkyl groups are particularly preferred. Each of the alkylgroups may contain from 1 to carbon atoms, preferably 2 to 6 carbonatoms and especially 4 carbon atoms. Furthermore, the alkyl groupscontained by any particular bisphenol may be the same or different andmay also be primary, secondary or tertiary alkyl groups. Bisphenolscontaining at least one tertiary alkyl group are particularly preferred.

The alkylated bisphenol may be prepared by any of the methods known inthe art of bisphenol manufacture, for example, by selecting theappropriate alkylated phenols as starting materials and condensing themtogether by any of the established methods. For example, alkylatedbisphenols may be prepared by the method described in US. Patent2,944,086.

As examples of the alkyalted bisphenols which may be used according tothe invention there are mentioned bis(3-ethyl 4 hydroxyphenyl)disulfide,bis(3-methyl-4- propyl 5 hydroxyphenyl) disulfide, bis(2 isopropyl-3-butyl-S-hydroxyphenyl) selenide, 2,2-diethy1 3 tertiarybutyl-4,4'-dihydroxydiphenyl selenide, bis 1,2(2,6-ditertiarybutyl-4-hydroxyphenyl)thiaethane, bis 1,2 (2,5-diisopropyl-3-hydroxyphenyl) ehiaethane, bis (3 ,5 -ditertiarybutyl-4-hydroxyphenyl)sulfide, 2,4 diisobutyl-3-hydroxybenzyl 2,4dipropyl 3 hydroxybenzyl sulfide, bis 1,2(3-octy1-5-tertiarybutyl-4-hydroxyphenyl)ethane, bis 1,1 (2,6-diisopropyl-4-hydroxyphenyl)ethane, 1,2-bis(2,4- ditertiary pentyl-3-hydroxyphenyl)propane, bis 2,2(4,5- ditertiary butyl-Z-hydroxyphenyl)propane, bis(2-tertiarybutyl-S-isopentyl 4 hydroxyphenyl)amine,bis(3,5-dibutyl-4-hydroxyphenyl)ether, bis(2,6-dipropyl-4-hydroxyphenyl)ether.

Preferred compounds are the alkylated bisphenols having a sulfur ormethylene bridge, the former include his (2,5 -dipentyl-4-hydroxyphenyl)sulfide, bis (2 ,5 -dihexyl- 3-hydroxyphenyl)sulfide,bis(2-methyl-5-tertiary butyl-4- hydroxyphenyl)sulfide,bis(2-methyl-5-tertiary butyl-6- hydroxyphenyl)sulf1de and particularlybis(3-tertiary butyl-S-methyl-Z-hydroxyphenyl) sulfide, and examples ofthe later, namely, alkylated bisphenols having a methylene bridgeinclude his (2,3-ditertiary butyl-4-hydroxyphenyl)- methane, bis (2,5-ditertiary butyl-4-hydroxyphenyl)methane, bis(2,6-ditertiarybutyl-4-hydroxyphenyl)methane, bis(3,5-ditertiary octyl-4-hydroxyphenyl)methane, bis(3- tertiary butyl-S-tertiary octyl-4-hydroxyphenyl)methane,and especially bis(3,5-ditertiary butyl-4-hydroxyphenyl)- methane.

Also the additive combinaton of the present invention appears to co-actwith certain phosphorus compounds to give additional unexpectedimprovement in anti-wear and anti-scuffing. Thus, this desirableimprovement can be imparted to lubricants of this invention by alsoincorporating a small amount (0.0l2%, preferably 0.11%) of a partial orfull ester of an organic phosphorus compound. Phosphorus compounds ofthis type include alkyl, cycloalkyl, alkaryl, aralkyl, and arylphosphites, phosphates, phosphonates, and their thio derivatives, suchas C alkyl phosphites e,.g., di and tributyl, octyl, lauryl, stearyl,

cyclohexyl, benzyl, cresyl, phenyl phosphite or phosphates, as well astheir thio derivatives; P S -terpcne reaction product, P S -pine oilreaction product and metal salts thereof such as Na, K, Ca or Ba saltsof P S -terpene reaction product; dibutyl methane-phosphonate, dibutyltrichloromethane phosphonate, dibutyl monochloromethane phosphonate,dibutyl chlorobenzene phosphnate, dibutyl monochloromethane phosphonate,dibutyl chlorobenzene phosphonate, and the like. The esters ofpentavalent phosphorus acids such as diphenyl, dicresyl, triphenyl,tricresyl, trilauryl and tristearyl ortho phosphates, P S terpenereaction products and mixtures thereof are preferred.

Minor amounts of each class of additives are sufficient for a highlyeffective combination. The nitrogen containing copolymer and theimidazoline salt may be used in an amount of about 01-10%, preferablyabout 0.2-5 by weight each of the lubricant, while about ODS-2%,preferably about 0.11% of the methylene bisphenol or sulfide derivativethereof is highly useful and about 0.1 2% of an organic phosphoruscompound.

The additive combinations of the present invention may be used toimprove various hydrocarbon lubricating oils, whether of natural originor synthetic, especially oils which are substantially paraffinic and/ ornaphthenic; they may contain substantial proportions of hydrocarbonshaving aromatic character but t e amounts and types of components shouldbe such that the Dean and Davis (Chem. and Met. Eng, vol. 36, 1929, pp.618-619) viscosity index of the base oil is at least 80, preferably atleast to 150.

The oil may be derived from a highly parafiinic crude, in which casedistillation and/ or dewaxing may be sufficient to provide a suitablebase stock; a minimum of chemical or selective solvent treatment may beused if desired. Mixed base crudes and even highly aromatic crudes whichcontain paratfinic hydrocarbons also provide suitable oil base stocks bywell known refining techniques. Usually these comprise the separation ofdistillate fractions of suitable boiling range followed by selectivesolvent extraction with solvents such as furfural, phenol and the liketo provide raflinate fractions which are suitable for further refiningby dewaxing and chemical treatment such as sulfuric acid treatment, etc.Thus, it may be a refined hydrocarbon oil obtained from a paraffinic,naphthenic, asphaltic or mixed base crude, and/ or mixtures thereof,such as SAE 5W, 10W, 20W, 20, 30, 40, 50 mineral oils. The hydrocarbonoils may be blends of different mineral oil distillates and brightstock; they may have blended therewith in minor but compatibleproportions fixed oils, such as castor oil, lard oil and the like and/orwith synthetic lubricants, such as polymerized olefins, e.g.polyisobutylene.

The following compositions are representative of the invention.

Composition A: Percent 1-aminoethyl-2-C alkyl imidazoline (NaloamineG32) dilau-ryl phosphate 1.4 Copolymer of N-vinyl pyrrolidone/laurylmethacrylate (M.W. 600,000)

Bis(3,5-ditert.butyl-4-hydroxyphenyl)rnethane 0.5 Mineral lubricatingoil (SAE 30) Balance Composition B:

Talimidazoline dilauryl phosphate 1.4 Copo lymer of N-vinylpyrrolidone/lauryl methacrylate (M.W. 600,000)

Bis(3,5-ditert.butyl-4-hydroxyphenyl)methane 0.5 Mineral lubricating oil(SAE 30) Balance Composition C:

1-aminoethyl-2-heptadecyl imidazoline dilauryl phosphate Copolyme-r ofN-vinyl pyrrolidone/lauryl methacrylateBis(3,S-ditert.butyl-4-hydroxyphenyl)methane 0.5 Mineral lubricating oil(10W30) Balance 7 Composition D:

1#fillliHOGthYl-Z-hfiPtfidCYl imidazoline dilauryl phosphate 2Copo-lymer of Example 11 5.5 Mineral lubricating oil (SAE 20) BalanceComposition E:

Nalcamine G-32 dilauryl phosphate 2 Copolymer of N-vinylpyrrolidone/lauryl methacrylate (Acryloid 917, Robin and Haas)-.. 5.5Bis(3,5-ditert.butyl-4-hydroxyphenyl)methane 0.5 Tricresyl phosphate 0.8Dicresyl phosphate 0.04

Mineral lubricating oil Balance Composition F:

Nalcamine G-32 dilauryl phosphate 1 Copolymer of Example I i 5.5Bis(3,5-ditert.butyl-4-hydroxyphenyl)methane 0.5 Tricresyl phosphate 0.8Dicresyl phosphate 0.04 Mineral lubricating oil Balance Otherrepresentative non-ash forming lubricating compositions of the presentinvention include mineral oil con taining:

G 25% copolymer of Example I+0.5% of salt (4), H2% copolymer of ExampleIl+0.25% of salt (7), I-5% of copolymer of stearyl methacrylate/laurylmethacrylate/2-methyl-5vinyl pyridine+0.75% salt (5), J4% of Acryloid917 copolymer+0.5% of salt (8 )+0.25 bis3-tert.butyl-5-methyl-2-hydroxyphen- K5% Acryloid 917 yl)methane.

In order to demonstrate the utility and improved propenties oflubricating compositions of this invention, the compositions identifiedin Table I were tested in (A) sequence II (rusting sequence) of GeneralMotors MS test described in AMA Proposed Test Procedure Minutes forMotor Oils for ASTM Test Procedures, Boston meeting, August 1958, (B)-L-4 engine test, (C) exhaust gas rust test (EGRT) which comprisesexposing oil-dipped steel panels to the exhaust vapors of a singlecylinder 4-cycle Briggs and Stratton engine operating on a high sulfurfuel. The panels are exposed to the hot exhaust gases for 30 minutes,then cooled to a temperature of F. for 16 hours and allowed to warm toroom temperature. The cycle is then repeated before inspection. Theamount of rusting is treated on a scale of l to 10, 10 being none and 1being heavy; (D) thermal stability test resides in storing a test sampleof oil in an oven for 60 hours at 275 F. and observing amount ofsedimentation or turbidity found and the results were as follows:

copolymer+=0.75 of salt methyl 2 hydroxyphen- Table I Tests A I B C DComposition L-4 EGRT Thermal (Rust Test (Rust- Stabil- Rating; (Finaling ity Test, =none; Rating: Rate: 60 hrs., 1=heavy) 100= 10=none; 275 Fperfect) 1=heavy) E--. 10 OK. D 9. 8 92. 4 8 OK. A 10 10 Sed. B 10 97. 310 OK. C l0 10 OK. (X) mineral oil (SAE 30) 5 copolymer of Ex. II 0.5%bis(3,5-ditert. butyl- 4-hydroxyphenyl)methane 5. 5 94. 7 1 OK. (X) 2%dilauryl acid phosh. e 6.0 95 4 Sod. (X) 1% Talimidazoline 5. 5 9s 3Sed.

.Lubhcatmg compositions of this invention are particularly applicablefor high temperature, high speed use as in aviation engines, automotiveengines and truck engines, as Well as industrial equipment operatingunder the conditions described in this invention.

We claim as our invention:

1. An improved mineral lubricating oil composition comprising a majoramount of mineral lubricating oil and from about 0.1% to about 10% eachof a copolymer of a polymerizable basic heterocyclic amine selected fromthe group consisting of vinyl pyridine and vinyl pyrrolidine and apolymerizable unsaturated material free of heterocyclicnitrogen-containing groups selected from the group consisting oflong-chain alkyl acrylates and long-chain alkyl methacrylates making amolecular weight of 200,000-800,000 and a C amino alkyl imidazoline saltof an hydrocarbyl acid phosphate, the hydrocarbyl radical being selectedfrom the group alkyl, aryl and cycloalkyl radicals said acid having from8 to 30 carbon atoms in the molecule.

2. An improved mineral lubricating oil composition comprising a majoramount of mineral lubricating oil and from about 0.1% to about 10% eachof la. copolymer of a vinyl pyridine and a long-chain alkyl methacrylatehaving a molecular Weight of 200,000-850,000 and a Cl-aminoalkyl-Z-alkyl imidazoline C dialkyl phosphate.

3. An improved mineral lubricating oil composition comprising a majoramount of mineral lubricating oil and from about 0.1% to about 10% eachof a copolymer of a vinyl pyrrelidone and a long-chain alkylmethacrylate having a molecular weight of 200,000-850,000 and a Cl-amino alkyl-Z-al-kyl imidazoline C dialkyl phospha-te.

4. An improved mineral lubricating oil composition comprising a majoramount of mineral lubricating oil and from about 0.1 o to about 10% eachof a copolymer of a vinyl pyridine and a long-chain alkyl methacrylatehaving a molecular weight of 200,000-850,000 and a C 1- aminoalkyl-2-alkyl imidazoline C1040 alkyl phosphonate.

5. An improved minenal lubricating oil composition comprising a majoramount of mineral lubricating oil and from about 0.1% to about 10% eachof a copolymer of a vinyl pyrrolidone and a lon -chain alkylmethacrylate having a molecular weight of 200,000-850,000 and a Cl-amino alkyl-2-alkyl imidazoline C1040 alkyl phosphonate.

6. An improved minenal lubricating oil composition comprising a majoramount of mineral lubricating oil and minor amounts of each of copolymerof Z-methyl-S-vinyl pyridine and a mixture of lauryl and stearylmethacrylate having a molecular weight of 200,000-850,000 and 1-aminoethyl-Z-heptadecyl imidazoline di'lauryl phosphate.

7. An improved mineral lubricating oil composition comprising a majoramount of mineral lubricating oil and minor amounts of each of acopolymer of vinyl pyrrolidone and lauryl methaorylate having molecularweight of 200,000-850,000 and 1-aminoethyl-2-heptadecyl imidazolinedilauryl phosphate.

8. The composition of claim 2 containing from about 0.1% to about 1% ofla bisphenol having the formula where X is a radical selected from thegroup consisting of CH and -S and R is a tertiary alkyl radical. 9. Thecomposition of claim 4 containing from about 0.1% to about 1% of abisphenol having the formula where X is a radical selected from thegroup consisting of -CH and S- and R is a tertiary alkyl radical. 10. Animproved mineral lubricating oil composition comprising a major amountof mineral lubricating oil and 2,285,853 Downing June 9, 1942 0.1% to10% each of copolymer of Z-methyl-S-vinyl pyri- 2,370,756 Sibley Mar. 6,1945 dine and a mixture of lau-ryl and stearyl methacrylates 2,728,644Vaughn Dec. 27, 1955 having a molecular weight of 200,000-850,000 and l-2,767,165 Smith et a1. Oct. 16, 1956 aminoethyl-Z-heptadecyl imidazolinedilauryl phosphate. 5 2,779,739 Spivack Jan. 29, 1957 11. An improvedmineral lubricating oil composition 2,798,045 Buck et a1. July 2, 1957comprising a major amount of mineral lubricating Oil and 2,846,440Hughes Aug. 5, 1958 0.1% to 10% each of copolymer of vinyl pyrrolidoneand 2 3 9 232 Lorensen et 1 J n 2 1959 lauryl methacryla-te having amolecular weight of 2,945,321 Steflin July 19, 19 0: 200,000850,000 and1 aminoethyl-2-heptadecyl imid'azo- 10 2,973,323 Millikan et Feb 28,1961 line dilauryl Phosphate 2,994,596 Sterlin Aug. 1, 1961 3,041,279Calhoun et al June 26, 1962 References Cited in the file of this patentUNITED STATES PATENTS FOREIGN PATENTS Re. 23,227- Blair et a1. May 9,1950 15 882,620 Great Britain Oct. 28, 1959

1. AN IMPROVED MINERAL LUBRICATING OIL COMPOSITION COMPRISING A MAJORAMOUNT OF MINERAL LUBRICATING OIL AND FROM ABOUT 0.1% TO ABOUT 10% EACHOF A COPOLYMER OF A POLYMERIZABLE BASIC HETEROCYCLIC AMINE SELECTED FROMTHE GROUP CONSISTING OF VINYL PYRIDINE AND VINYL PYRROLIDINE AND APOLYMERIZABLE UNSATURATED MATERIAL FREE OF HETEROCYCLICNITROGEN-CONTAINING GROUPS SELECTED FROM THE GROUP CONSISTING OFLONG-CHAIN ALKYL ACRYLATES AND LONG-CHAIN ALKYL METHACRYLATES MAKING AMOLECULAR WEIGHT OF 200,000-800,000 AND A C1-4 AMINO ALKYL IMIDAZONLINESALT OF AN HYDROCARBYL ACID PHOSPHATE, THEHYDROCARBYL RADICAL BEINGSELECTED FROM THE GROUP ALKYL, ARYL AND CYCLOALKYL RADICALS SAID ACIDHAVING FROM 8 TO 30 CARGON ATOMS IN THE MOLECULE.